Coupled processes involving ammonium inputs, microbial nitrification, and calcite dissolution control riverine nitrate pollution in the piedmont zone (Qingshui River, China).

Rivers in agricultural countries widely suffer from diffuse nitrate (NO3-) pollution. Although pollution sources and fates of riverine NO3- have been reported worldwide, the driving mechanisms of riverine NO3- pollution associated with mineral dissolution in piedmont zones remain unclear. This study combined hydrogeochemical compositions, stable isotopes (δ18O-NO3-, δ15N-NO3-, δ18O-H2O, and δ2H-H2O), and molecular bioinformation to determine the pollution sources, biogeochemical evolution, and natural attenuation of riverine NO3- in a typical piedmont zone (Qingshui River). High NO3- concentration (37.5 ± 9.44 mg/L) was mainly observed in the agricultural reaches of the river, with ~15.38 % of the samples exceeding the acceptable limit for drinking purpose (44 mg/L as NO3-) set by the World Health Organization. Ammonium inputs, microbial nitrification, and HNO3-induced calcite dissolution were the dominant driving factors that control riverine NO3- contamination in the piedmont zone. Approximately 99.4 % of riverine NO3- contents were derived from NH4+-containing pollutants, consisted of manure & domestic sewage (74.0 % ± 13.0 %), NH4+-synthetic fertilizer (16.1 % ± 8.99 %), and soil organic nitrogen (9.35 % ± 4.49 %). These NH4+-containing pollutants were converted to HNO3 (37.2 ± 9.38 mg/L) by nitrifying bacteria, and then the produced HNO3 preferentially participated in the carbonate (mainly calcite) dissolution, which accounted for 40.0 % ± 12.1 % of the total riverine Ca2+ + Mg2+, also resulting in the rapid release of NO3- into the river water. Thus, microbial nitrification could be a new and non-negligible contributor of riverine NO3- pollution, whereas the involvement of HNO3 in calcite dissolution acted as an accelerator of riverine NO3- pollution. However, denitrification had lesser contribution to natural attenuation for high NO3- pollution. The obtained results indicated that the mitigation of riverine NO3- pollution should focus on the management of ammonium discharges, and the HNO3-induced carbonate dissolution needs to be considered in comprehensively understanding riverine NO3- pollution in piedmont zones.

Tracing nitrate origins and transformation processes in groundwater of the Hohhot Basin's Piedmont strong runoff zone through dual isotopes and hydro-chemical analysis.

Nitrate, which poses a serious threat to the drinking water supply, is one of the most prevalent anthropogenic groundwater contaminants worldwide. With the development of the chemical industry, the nitrate pollution of groundwater in the Piedmont strong runoff zone of the Hohhot Basin, which is the main groundwater extraction area, is becoming increasingly severe. The special hydrogeological and complex pollution conditions in the study area make it difficult to identify nitrate sources and transformation processes. In order to identify the results more accurately, this study combined water chemistry, multivariate statistical analysis and isotope tracer methods to determine the sources and transformation processes of nitrate in the study area. The results showed that the groundwater in the eastern part of the study area (ESA) was clearly affected by anthropogenic activities, and its nitrate was mainly from nitrification of ammonia in industrial wastewater, nitrate in industrial wastewater (the sum of the two contributions was 62.2 %), and nitrate in manure (20.5 %). The hydrogeochemical characteristics of groundwater in the western part of the study area (WSA) are the same as those of natural groundwater in the Piedmont strong-runoff zone. The nitrate in groundwater in the WSA was mainly derived from soil nitrogen (63.8 %) and ammonia fertilizer (28.8 %). Nitrification and denitrification occurred only locally in the aquifer of the study area and were more pronounced in the ESA. Meanwhile, the transformation processes of nitrate in groundwater in the ESA and WSA was significantly influenced by contamination with chlorinated hydrocarbon volatile organic compounds and hydrogeological conditions, respectively. These findings provide a scientific basis for the development of groundwater pollution prevention measures in the study area and guide the traceability of nitrate in groundwater in areas with similar hydrogeological and pollution conditions.

Identification of ammonium source for groundwater in the piedmont zone with strong runoff of the Hohhot Basin based on nitrogen isotope.

Groundwater with high ammonium concentration (HANC groundwater), mostly caused by anthropogenic pollution, is widely distributed in China, which could also result from natural geological genesis. Groundwater in the piedmont zone with strong runoff in the central Hohhot Basin has featured its excessive ammonium concentration since the 1970s. Currently, chemical factories also serve as potential pollution sources. In this study, based on the nitrogen isotopic technique and combined with hydrochemical methods, the sources of high concentration ammonium in the groundwater was identified. The HANC groundwater is mainly distributed in the alluvial-proluvial fan and the interfan depression in the western and central parts of the study area, and a maximum ammonium concentration of 529.32 mg/L was observed in the groundwater in the mid-fan of the Baishitou Gully (BSTG) alluvial-proluvial fan. Although the BSTG mid-fan is part of the piedmont zone with strong runoff, some of the HANC groundwater in this area still presents the typical hydrochemical characteristics in the discharge area. Moreover, an extremely high concentration of volatile organic compounds was observed in groundwater in the BSTG alluvial-proluvial fan, which indicated significant anthropogenic pollution. Besides, 15N-NH4+ is enriched in groundwater in the BSTG root-fan and the interfan depression, which is consistent with the situation of organic nitrogen and exchangeable ammonium in natural sediments, as well as the natural HANC groundwater in other regions of China. These δ15N-NH4+ values indicate that the ammonium of the groundwater in the BSTG root-fan and the interfan depression is derived from natural sediments. The 15N-NH4+ in groundwater is depleted in the BSTG mid-fan, and the δ15N-NH4+ values are similar with those of the pollution sources from the chemical factories in the mid-fan. Both hydrochemical and nitrogen isotopic characteristics indicate significant pollution in the mid-fan, but the ammonium pollution is limited to the area near the chemical factories.

The distribution characteristics and geological control factors of shallow high-arsenic groundwater in the Hetao Plain, Inner Mongolia, from the perspective of Late Pleistocene-Holocene depositional environments.

The alluvial-lacustrine strata that were formed by the evolution of rivers and lakes in the Hetao Plain during the Late Quaternary have an important influence on the formation and distribution of shallow high-arsenic groundwater. This study analyzed the distribution characteristics and depositional environments of shallow high-arsenic groundwater in study area using 1179 groundwater samples and more than 1100 pieces of drilling data. The indicator kriging statistics and the study results of the Quaternary lithofacies paleogeography show that the study area can be divided into three high-arsenic probabilistic distribution areas, namely, the Houtao Plain (HTP), the Yellow River Channel Belt (YRCB), and the Eastern Hubao Plain (EHBP). The depositional environment of the HTP was shaped by the alluviation of the Yellow River during the Late Pleistocene-Holocene. The YRCB is still affected by the alluviation of the Yellow River presently, and the EHBP was almost unaffected by the Yellow River. The high-arsenic groundwater in the EHBP is mostly distributed in the relatively continuous alluvial-lacustrine strata and has a typical hydrochemical type of HCO3, with the highest Meq(HCO3-/SO42-) and the highest reduction degree of SO42-. By contrast, the high-arsenic groundwater in the alluvial-lacustrine environments of the HTP and the YRCB accounts for only 14.77% and 20.13%, respectively, and has only less than 40% of HCO3 dominant type water. The high-arsenic groundwater in these two areas is generally located in the alluvial or alternating fluvial-lacustrine strata. However, the two areas exist more than three alluvial-lacustrine layers with a thickness of over 2 m each, which play a critical role in the formation of high-arsenic groundwater. Moreover, affected by alluvial aquifers in the same system, the high-arsenic groundwater in both the HTP and the YRCB is not intensively distributed and does not represent a typical HCO3 dominant type. The S2- produced by the massive reduction of SO42- might co-precipitate with Fe and As, which may explain why the EHBP has lower arsenic concentration than the HTP and the YRCB, both of which have a lower reduction degree of SO42-.

Effects of Co-Inoculating Saccharomyces spp. with Bradyrhizobium japonicum on Atmospheric Nitrogen Fixation in Soybeans (Glycine max (L.)).

Crop production encounters challenges due to the dearth of nitrogen (N) and phosphorus (P), while excessive chemical fertilizer use causes environmental hazards. The use of N-fixing microbes and P-solubilizing microbes (PSMs) can be a sustainable strategy to overcome these problems. Here, we conducted a greenhouse pot experiment following a completely randomized blocked design to elucidate the influence of co-inoculating N-fixing bacteria (Bradyrhizobium japonicum) and PSMs (Saccharomyces cerevisiae and Saccharomyces exiguus) on atmospheric N2-fixation, growth, and yield. The results indicate a significant influence of interaction on Indole-3-acetic acid production, P solubilization, seedling germination, and growth. It was also found that atmospheric N2-fixation, nodule number per plant, nodule dry weight, straw, and root dry weight per plant at different growth stages were significantly increased under dual inoculation treatments relative to single inoculation or no inoculation treatment. Increased seed yield and N and P accumulation were also noticed under co-inoculation treatments. Soil available N was highest under sole bacterial inoculation and lowest under the control treatment, while soil available P was highest under co-inoculation treatments and lowest under the control treatment. We demonstrated that the co-inoculation of N-fixing bacteria and PSMs enhances P bioavailability and atmospheric N2-fixation in soybeans leading to improved soil fertility, raising crop yields, and promoting sustainable agriculture.

Ionic structure and transport properties of KF-NaF-AlF3 fused salt: a molecular dynamics study.

We used the first-principles molecular dynamics simulations combined with the interatomic potential molecular dynamics to study the ionic structure and transport properties of KF-NaF-AlF3 fused salt. Simulation results show that the ionic structure of KF-NaF-AlF3 fused salt is principally dominated by the distorted five-coordinated [AlF5]2- and six-coordinated [AlF6]3- groups. When melting to a liquid, a part of the six-coordinated [AlF6]3- group dissociated into the four-coordinated [AlF4]- and five-coordinated [AlF5]2- groups. Four, five and six-coordinated aluminum-fluoro complexes coexist in KF-NaF-AlF3 fused salt, while the tetrahedral [AlF4]- groups are relatively rare. The content of the bridging fluorine atom is relatively small, about 5-11%, which indicates that the polymerization degree of the ionic structure of the KF-NaF-AlF3 fused salt system is lower. The KF-NaF-AlF3 fused salt has better liquidity and ionic conductivity due to the high self-diffusion coefficients of all particles in the fused salt system. KF can effectively break the F atom bridges, which reduces the polymerization degree of the ionic structure of the fused salt system and increases its ionic conductivity.